Chemical compounds containing sulfur and spirobi (meta-dioxane) groups



No Drawing. Filed Sept. 26, 1957. Ser. No. 686,277

- 8 Claims. (Cl. 260-3405) This invention relates to novel spirobi(meta-dioxane) derivatives and their preparation. In one aspect, this invention relates to a method of producing chemical compounds containing spirobi(meta-dioxane) and sulfur groups. In another aspect, this invention relates to chemical compounds containing substituted spirobi(metadioxane) and sulfur groups which are useful as intermediate reactants and as accelerators for curing rubber.

It is an object of the present invention to provide a method for producing chemical compounds containing spirobi(meta-dioxane) and sulfur groups.

It is a further object of this invention to provide spirobi(meta-dioxane)- and sulfur-containing chemical compounds which have active sites that can react under suitable conditions.

Other objects and advantages of the present invention will become apparent to those skilled in the art from the following description.

The compounds according to this present invention are produced by reacting together a 3,9-divinylspirobi(metadioxane) compound and a mercaptoalcohol having available at least one thiol group and one hydroxyl group.

The 3,9-divinylspirobi(meta-dioxane) compounds preferred are those having the formula:

CHQQ

C CHiO wherein D is selected from the group consisting of (R-CH=CH-) and R (OHFJJ-Q and R is selected from the group consisting of hydrogen,v halogen and lower alkyl.

The 3,9-divinylspirobi(meta dioxan'e) compounds which are most conveniently and economically prepared from widely available starting materials are those which have hydrogen or a methyl substituted on each vinyl group. The 3,9-divinylspirobi(meta-dioxane) compounds which contain groups other than hydrogen and methyl substituted on the vinyl groups are sometimes more difiiicult to prepare. These other groups must be of a character and in a position on the vinyl groups not to interfere with the effective reactions of 3,9-divinylspirobi- (metadioxane) compounds in the process of the present invention.

3,9-divinylspirobi(metardioxane) compounds which contain a terminal methylene group are of. particular advantage for ease of reaction, quality of product, etc. Their use, therefore, generally is the most preferred. Substituents on the vinyl groups. of a spirobitmet'a-dioxane) nucleus may be included to alter thepropertie's of the product compounds and/or to act as reactive sites for chemical transformation of the products under suitable conditions.

, t6 States Patent? The preferred 3,9-divinylspirobi(meta-dioxane) start- 0 ing materials of this present inventionmay be prepared by the condensation of a mole of pentaerythritol with two. moles of acrolein. or an, acrolein. derivative in the presence of an acid catalyst such asp-toluenesulfonic acid. This well-known synthetic method is published in "ice OCH:

When the condensation is conducted with (a) alphamethyl acrolein or (b) crotonaldehyde, then methylsubstituted- 3,9-divinylspirobi(meta-dioxanes) are obtained:

(a) CH; HO OH: ECEfiC CHO+ /C HOCH:

OHsOH CHsOH on. ,0 cm

CHFQ CH C (5) HO CH2 2GHiCH=CHCHO+ o I HOG a 0320B /0 CH1 CHZO C CHaO CH3 /CHO=CH: (EH20 OHIOH CHsCH=CECH /CHOH=CHCHa OCHz CHzO It is not necessary that the 0:,[3-11I1Stitll1'3t6d aldehyde reacted with pentaerythritol be pure or a single species. Mixtures of cap-unsaturated aldehydes may be condensed with pentaerythritol for purposes of convenience and economy. The resulting products are mixtures of 3,9- divinylspirobi(meta-dioxane) compounds which may be used in their crude form directly in the processes of this invention.

The mercaptoalcohols that are useful in this invention are those which contain at least one thiol group and one hydroxyl group and not more than 10 carbon atoms. The wide variety of mercaptoalcohols that may be reacted with 3,9-divinylspirobi(meta-dioxane) compounds can be illustrated by a representative group comprising monothioethyleneglycol (Z-mercaptoethanol); monothi'o} diethyleneglycol; Z-mercapto-l-propanol; l-thiog'lycer'ol; 1,2-dithioglycerol; 1,3-dithioglycerol; 3-ethoxy-1,2-dimercaptopropane; l-chloro-2-hydroxy-3-mercaptopropone; 2- mercaptoimidazo'ethanol; mercaptophenol; dimercaptophenol; trimercaptophenol; and trimercaptoresorcinol.

Mercaptoalcohols are easily synthesized either by the reaction of an alkylene oxide with hydrogen sulfide or by the reaction of a haloalcohol with a metal mercaptan. Epoxy alcohols and epoxy halides also may be converted to mercaptoalcohols. p,

The reaction of a mercaptoalcohol and a 3,9-divinylspirobi(meta-dioxane) compound proceeds well under moderate conditions. The reaction temperature may vary between about room temperature and 200 C., with a-preferredtemperature range being between and C. Atmospheric pressure is satisfactory for most of the reactions, or autogenous pressure if the reaction is conducted in a closed system. Either batchwise or continuous 3 4 methods may be employed. The reaction time may vary taining compounds can be imparted to other materials between about 0.1 and 20 hours depending on the nature such as natural and synthetic polymers and elastomers of the reactants and on the reaction conditions. by mixture or combination of the sulfur-containing com- The mole ratio of mercaptoalcohol to 3,9-divinylpounds with said materials. spirobi(meta-dioxane) may vary between 5 moles of 5 The following examples will serve to illustrate particumercaptoalcohol to each mole of spirobi compound, and lar embodiments of this invention.

0.5 mole of mercaptoalcohol to each mole of spirobi compound. An excess of mercaptoalcohol compound favors a simple addition product, while an excess of 3,9- EXAMPLE 1 divinylspirobi(meta-dioxane) increases the possibility of a OCH7 Cmo polymerization reaction, the latter being especially. true at higher temperatures and in the presence of an acid catalyst CHFCE c HCCHCHZ+HO OHiCHtsH such as p-toluenesulfonic acid, sulfuric acid, and zinc 0C a 01120 chloride. 3,9-dlvinylspirobl(meta-dloxaue) monothioethylene- A solvent is not ordinarily necessary but if it is desired gg one may be employed, e.g., benzene, dioxane, tetrahydro- O CH, CHZO furan, ethyleneglycol diether ether, dibutyl ether, heptane, 1 dimethylformamide, and the like. A solvent may be C HCCtHtsCHtCHtOH preferable when an inorganic acid catalyst is being used. i H, 3,

AH illustratlon 0t t Produetlell the nevel 3,9 -bls(Z-hydroxyethylmercaptoethyl)spirobl(meta-dioxane) pounds of this invention is the reaction of 1,3-dith1oglycerol with 3,9-(a,oU-dimethyl)divinylspirobi(metad1oxane) under conditions which favor polymerization: 3 A mixture of 3,9-divinylspirobi(meta-dioxane) (42 CH: OCHQ CHzO CH5 I I v HOCH(CE2SH)2+CH2=CCH O HCC=GH:

0cm cmo I r a n1 i o'ogi omo on HSCHaCHCH2S--C2HCH CCzHeBCHgHCH:B-H I L OCH: CHaO In Another illustration is the reaction of monothiodiethylgrams, 0.2 mole) and monothioethyleneglycol (31 grams, eneglycol with 3,9-(B,B'-dimethyl)divinylspirobi(meta-div 0.4 mole) were introduced into a glass reaction flask oxane) under conditions which yield addition products: 35 equipped with a stirrer and' a reflux condenser and HSCHZCHM)CH2CH2OH+OH3CH:CH R CH=CHCH3+ at 8. temperature of 120I fOI'.O]1e hour. The

tillation, and a residual product (66 grams) was ob- HOCHZGHZOCHCHZSTCQHFRTQETOCHCHOCH'OHSH tained which had-11 1.5364, a molecular weight of wherein 40 350 by the Menzies-Wright method (theory for product 0013, 011,0 formula above: 368), and 103.1% purity* by analytical is 'phthalation (determines both hydroxyl and thiol groups).

/ An 'analysis of thiol groups by oxidation with iodine was 00 performed and it indicated that 32.8% by weight of The mercaptoalcohol reactans described in this inventhe product was 3,9-bis(2-rnercaptoethoxyethyl)-spirobition have at least two functional positions, i.e., a thiol (meta-dioxane). These results show that about twogroup and a hydroxyl group. As mentioned previously, v thirds of the double bonds in the divinyl compounds simple addition or polymerization may occur. When added the thiol group and approximately one-third added only one mercaptan group is present in the mercaptothe hydroxyl group alcohol then addition reactions predominate. Whentwo v or more mercaptan groups are present then polymeriza- EXAMPLE 2 tion may be induced more easily. This is due to the difference in reactivity of the hydroxyl group and the 90% 39'd1vmY1sP1mb1(meta-(hexane) (236 grams' mercaptan group. The hydroxyl group is a weaker base mole) p'toluenesulfon.lc acid catalysit gram) ihan the mercaptan group, ie the mercaptan group is were placed in a glass reaction flask equipped with a more nucleophilic than the hydroxyl group, hence, a Smrer feed tank 3 q p i and heated. at a mercaptan group more readily forms a bond with an electemperature of 90 wlth Surfing Monothloeih' tron-deficient carbon atom than does a hydroxyl group. ylengglycol (15 grams mole?) was added to the W From the foregoing description it is apparent that com- P over a Penod of thirty mmutes- After a Yemen plex product mixtures may result from the reaction of a tlme of Seven hours at a temperature of the aeld mercaptoalcohol with a 3,9-divinylspirobi(meta-dioxane). t y Was neutralized y the addition of anhydrous The potential or actual variety of products is due to the 1 sodium acetate (3.0 grams), and the reaction mixture polyfunctionality of the reactants, and also due to the components which were volatile at a kettle temperature fact that there are two modes of addition to each of the of 89 C ./3 mm, were removed by distillation to yield vinyl groups in the spirobKmeta-dioXane) compound a residualproduct 345 grams) which had a molecular which increases the number of possible isomers. weigh v of 1 the Menzies wright h d The products of this invention have wide application in e E the chemical field. The unique properties exhibited by Q EXAMPLE 3 these sulfur-containing spirobi(meta-dioxane) derivatives I make them applicable as accelerators for curing rubber Thls example Illustrates the etteetlve use of a Product and as intermediates for the production of other chemof this invention an aeeelefatol' the vulcanization icals. The reactive sites, e.g., hydroxyl, mercaptan, sulf natural rubber.

fide, acetal, etc., make the compounds susceptible to chern- 1 i631 transformation. *Pereentages slightly higher than one hundred are not in- The properties of these liquid and solid sulfur-conusual results for some analytical procedures.

Formulations compounded minutes at 75 to 90 C. on a two-roll mill (a) 100 grams natural rubber (smoked sheet) 1 gram Age Rite powder 5 grams zinc oxide 2 grams sulfur 3 grams stearic acid 50 grams Kosmobile 77EPC carbon black (b) Same as (a) except 1 gram of the product described in Example 2 was added.

Both (a) and (b) were cured (vulcanized) for 60 minutes at 140 C. in 5% inch positive molds. The cured compositions had the following properties:

Tensile, p.s.i 380 1, 200 Elongation, percent 375 420 Load at 300% elongation, p.s.i 200 675 Hardness, Durometer A 14 45 ASTM Stifiness Modulus, p.s.i 6, 700

1 Too soft and flexible for testing.

Having described our invention, we claim: 1. A composition of matter having the formula:

0 OH: CH2O\ HooHiomsoiHiofi 0 HCOiHisomoHmH 2. A composition of matter having the formula:

00H: omo HOCHICHflSOflHOfi 0 ooimo oHmHisH 0C 2 CHRO 3. A composition of matter having the formula:

00H, 011,0 HSCHzCHaO oiHiofi 0\ E0 (limo OHQOHiSH 00 CHEO 6 4. A composition of matter having the formula:

00H: OHIO CH2=CHCH /0 EC CQHLSCHICHBOH O CH: CHHO wherein D is selected from the group consisting of (RCH=CH-) and CHzO and R is selected from the group consisting of hydrogen, halogen and lower alkyl.

7. The process of claim 6 wherein said mercaptoalkanol is Z-mercaptoethanol.

8. The process of claim 7 wherein said 3,9-diviny1- spirobi(meta-dioxane) derivative is 3,9-divinylspirobi (meta-dioxane) References Cited in the file of this patent UNITED STATES PATENTS 2,150,425 Cramer Mar. 14, 1939 2,343,566 Mathes Mar. 7, 1944 2,399,068 Senkus Apr. 23, 1946 2,525,681 Jones et a1. Oct. 10, 1950 2,709,715 Heller May 31, 1955 

1. A COMPOSITION OF MATTER HAVING THE FORMULA: 